Froome, who finished behind team-mate Bradley Wiggins in France last month, has named in the nine-man line-up for the Spanish Grand Tour alongside fellow Britons Ian Stannard and Ben Swift.
Olympic road race silver medallist Rigobero Uran, Juan Antonio Flecha, Sergio Henao, Danny Pate, Richie Porte and Xabier Zandio complete the team.
Froome finished second in the 2011 Vuelta, one place ahead of Wiggins, and will be expected to challenge Alberto Contador, the former Tour de France champion who is returning from a doping ban, for the overall title.
"It's always been my plan to ride the Vuelta," the 27-year-old, who recently won bronze in the Olympic time trial, said.
"I'll be going into the race as team leader but that's not to say we don't have other guys who can be right up there on the GC (general classification).
"Rigoberto and Sergio both have huge potential, and Richie is another guy who could shine.
"I'm going to do the best job I can and do whatever's required of me from the team.
"Initially I'll be riding for the GC, but if one of my team-mates shows that they're in a better place to win the race then I'll happily work for them.
"We're sending a first-rate squad and it should be a really exciting race."
Swift is the nominated sprinter.
He added: "I'm really excited about being the team's main sprinter. There should be plenty of opportunities for me and I'll be doing my best to get my first Grand Tour stage win."
The race begins on August 18 and finishes on September 9.